KR20110055441A - Aqueous coating composition - Google Patents

Abstract

PURPOSE: An aqueous coating composition is provided to increase crosslinking density and to improve resistances to scratch, damage and crack, and durability. CONSTITUTION: An aqueous coating composition comprises (a) at least one of calcium ion and magnesium ion, and (b) a polymer containing a polymerized moiety and having Tg 50-110 °C. The polymerized moiety comprises (b-1) 0.5-7 wt% of one or more monomers in which an index stability constant for calcium or magnesium is 0.3-4, (b-2) 5-15 wt% of methacrylic acid, and (b-3) 0.2-3 wt% of one or more cross-linking agents.

Description

Aqueous coating composition {AQUEOUS COATING COMPOSITION}

FIELD OF THE INVENTION The present invention relates to aqueous coating compositions, and more particularly to aqueous coating compositions useful as floor finishes.

Aqueous coating compositions for floors and other surfaces have traditionally used transition metal ions, such as zinc, to add to the crosslinks. Most recent efforts have focused on using more environmentally acceptable metal ions such as calcium and magnesium as ionic crosslinkers. For example, US Patent Application Publication No. 2007/0254108 describes a composition using calcium. However, none of the prior art compositions using calcium or magnesium provide a combination of properties that meet commercial needs.

The problem posed by the present invention is to provide an aqueous coating composition using calcium or magnesium as the ionic crosslinker.

The present invention provides an aqueous coating composition comprising a polymer, the polymer comprising (a) at least one of calcium ions and magnesium ions; (b) (i) 0.5 to 7 wt% of at least one monomer having a log stability constant of 0.3 to 4 for calcium or magnesium; (ii) 5 to 15 wt% methacrylic acid; And (iii) a polymerized moiety consisting of 0.2 to 3 wt% of at least one crosslinker, wherein the Tg of the polymer is from 50 to 110 ° C.

The present invention also relates to a method of coating a substrate by applying the aqueous coating composition to the substrate.

Unless otherwise specified, the percentage is percent by weight (wt%), the temperature is in degrees Centigrade, and the stability constant is measured at ambient temperature (typically 20 to 25 degrees C). The weight percentage of monomers is based on the total weight of monomers in the polymerization mixture. Tg values of all polymers were measured by differential scanning calorimetry (DSC) using a heating rate of 10 ° C. per minute and the Tg was taken at the midpoint of the transition.

As used herein, "[meth] acrylic" refers to acrylic or methacrylic, and "(meth) acrylate" refers to acrylate or methacrylate. "(Meth) acrylamide refers to acrylamide (AM) or methacrylamide (MAM)." Acrylic monomer "refers to acrylic acid (AA), methacrylic acid (MAA), esters of AA and MAA, itaconic acid (IA ), Crotonic acid (CA), acrylamide (AM), methacrylamide (MAM), and derivatives of AM and MAM, such as alkyl (meth) acrylamides. But not limited to, alkyl, hydroxyalkyl, phosphoalkyl and sulfoalkyl esters, for example methyl methacrylate (MMA), ethyl methacrylate (EMA), butyl methacrylate (BMA), isobutyl meta Acrylate (iBMA), hydroxyethyl methacrylate (HEMA), hydroxyethyl acrylate (HEA), methyl acrylate (MA), ethyl acrylate (EA), butyl acrylate (BA), ethylhexyl acrylate (EHA), phosphoethyl methacrylate (PAM), and the like. Refers to monomers comprising carbon-carbon double bonds bonded to heteroatoms such as nitrogen or oxygen, etc. Examples of vinyl monomers include, but are not limited to, vinyl acetate, vinyl formamide, vinyl acetamide, vinyl pyrrolidone, Long chain vinyl alkanoates such as vinyl caprolactam and vinyl neodecanoate and vinyl stearate, etc. “Aromatic-acrylic polymer” refers to polymers of acrylic monomers and vinyl aromatic monomers or vinyl cyclohexyl monomers. Vinyl aromatic monomers have one ethylenically unsaturated group per molecule Examples of vinyl aromatic monomers include 4-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methoxystyrene, 2- Hydroxymethylstyrene, 4-ethylstyrene, 4-ethoxystyrene, 3,4-dimethylstyrene, 2-chlorostyrene, 3-chlorostyrene, 4-chloro-3-methylstyrene, 4 -t-butylstyrene, 2,4-dichlorostyrene, 2,6-dichlorostyrene, 1-vinylnaphthalene, cyclohexyl methacrylate, benzyl methacrylate, benzyl acrylate, etc. Preferred vinyl aromatic monomers are vinyl Pyridine, styrene (Sty) and 4-methylstyrene (vinyltoluene). "Styrene-acrylic polymer" refers to a copolymer of acrylic monomers and at least 50% of acrylic monomers, styrene and vinyl toluene. Preferably, the styrene-acrylic polymer comprises at least 75%, more preferably at least 85% and most preferably at least 95% of monomer residues derived from (meth) acrylic acid, (meth) acrylate or styrene. Preferably, the remaining monomers are derived from vinyl monomers.

For the purposes of the present invention, the alkyl group is a straight chain or branched alkyl group or an alkyl carbocyclic group such as an aralkyl or alkylphenyl group. In some embodiments of the invention, the alkyl group is synthesized and may contain a range of chain lengths. In some embodiments of the invention, the alkyl group is a straight or branched chain acyclic alkyl group.

The aqueous coating composition comprises calcium ions, magnesium ions or combinations thereof. In some embodiments of the invention, the composition is substantially free of transition metal ions, for example less than 0.5%, optionally less than 0.2%, optionally less than 0.1%, optionally less than 0.05%. In some embodiments of the invention, the composition comprises at least 0.1 equivalents, optionally at least 0.15 equivalents, optionally at least 0.2 equivalents, optionally at least 0.23 equivalents of calcium and / or magnesium per equivalent of acid in the polymer; In some embodiments, the composition comprises up to 0.7 equivalents, optionally up to 0.6 equivalents, optionally up to 0.5 equivalents, optionally up to 0.4 equivalents, optionally up to 0.4 equivalents, optionally up to 0.35 equivalents, per 1 equivalent of acid and calcium in the polymer It contains. The equivalent of acid in the polymer is calculated from the total amount of acid, such as carboxylic acid groups, phosphonate groups, in the polymer. In some embodiments of the invention, the composition comprises calcium.

In some embodiments of the invention, the polymer further comprises monomeric residues of C ₁ -C ₈ alkyl (meth) acrylates. In some embodiments of the invention, the C ₁ -C ₈ alkyl (meth) acrylate comprises alkyl methacrylate and alkyl acrylate, optionally C ₁ -C ₂ alkyl methacrylate (MMA or EMA) And C ₄ -C ₈ alkyl acrylates (eg BA or EHA), optionally MMA, and C ₄ -C ₈ alkyl acrylates, optionally MMA and BA. In some embodiments of the invention, the total amount of C ₁ -C ₈ alkyl (meth) acrylate monomer residues is from 34% to 70%. In some embodiments, the total amount of C ₁ -C ₈ alkyl (meth) acrylate monomer residues is at least 36%, optionally at least 38%, optionally at least 40%, optionally at least 42%, optionally at least 44%, optional By 46% or more, optionally 48% or more. In some embodiments, the total amount of C ₁ -C ₈ alkyl (meth) acrylate monomer residues is at most 68%, optionally at most 66%, optionally at most 64%, optionally at most 62%, optionally at most 60%. In some embodiments of the invention, the Tg of the polymer is at least 55 ° C, optionally at least 60 ° C, optionally at least 65 ° C, optionally at least 70 ° C, optionally at least 75 ° C, optionally at least 80 ° C; In some embodiments the Tg is at most 105 ° C, optionally at most 100 ° C, optionally at most 95 ° C, optionally at most 90 ° C, optionally at most 85 ° C. Those skilled in the art can select monomers to reach the desired Tg value. The identity and amount of each of the monomers is not critical if the Tg is within the above range.

In some embodiments of the invention, the polymer comprises one or more monomers, the monomers having an index stability constant of at least 0.4, optionally at least 0.5, for calcium or magnesium. In some embodiments of the invention, the index stability constant for calcium or magnesium is at most 3.5, optionally at most 3, optionally at most 2.5, optionally at most 2, optionally at most 1.5. In some embodiments of the present invention, the monomer has an exponential stability constant for calcium within the above range. In some embodiments of the invention, the polymer comprises at least 0.7%, optionally, of polymerized moieties of at least one monomer (complexing monomer) having an exponential stability constant for calcium or magnesium within the above-mentioned ranges. At least 0.9%, optionally at least 1.1%, optionally at least 1.3%, optionally at least 1.5%, optionally at least 1.6%, optionally at least 1.7%; In some embodiments, the polymer comprises up to 6.5%, optionally up to 6%, optionally up to 5.5%, optionally up to 5%, optionally up to 4.5%, optionally up to 4% of the polymerized moieties of at least one complexing monomer Or less, optionally 3.5% or less, optionally 3% or less, optionally 2.5% or less. In some embodiments of the invention, the complexing monomer is acrylic acid, itaconic acid or a combination thereof.

In some embodiments of the invention, the polymer contains at least 6%, optionally at least 7%, optionally at least 8%, optionally at least 9% of polymerized moieties of methacrylic acid; In some embodiments, the polymer contains 14% or less, optionally 13% or less, optionally 12% or less, polymerized moiety of methacrylic acid.

In some embodiments of the invention, the polymer contains 25 to 50 wt% of one or more vinyl aromatic monomers. In some embodiments, the polymer contains at least 28%, optionally at least 30%, optionally at least 32% of polymerized moieties of at least one vinyl aromatic monomer; In some embodiments, the polymer contains up to 45%, optionally up to 42%, alternatively up to 40%, optionally up to 38% of polymerized moieties of one or more vinyl aromatic monomers. In some embodiments of the invention, the polymer comprises a styrene moiety.

Crosslinkers are monomers having two or more ethylenically unsaturated groups, for example divinylaromatic compounds, di-, tri- and tetra- (meth) acrylate esters, di-, tri- and tetra-allyl ethers or ester compounds and Allyl (meth) acrylate and the like. Preferred examples of such monomers include divinylbenzene (DVB), trimethylolpropane diallyl ether, tetraallyl pentaerythritol, triallyl pentaerythritol, diallyl pentaerythritol, diallyl phthalate, diallyl maleate, triallyl Cyanurate, bisphenol A diallyl ether, allyl sucrose, methylene bisacrylamide, trimethylolpropane triacrylate, allyl methacrylate (ALMA), ethylene glycol dimethacrylate (EGDMA), hexane-1.6-diol di Acrylate (HDDA) and butylene glycol dimethacrylate (BGDMA). Particularly preferred crosslinkers are DVB, ALMA, EGDMA, HDDA and BGDMA and the like. In some embodiments of the present invention, the amount of polymerized crosslinker moiety in the polymer is at least 0.3%, optionally at least 0.4%, optionally at least 0.5%, optionally at least 0.6%, optionally at least 0.7%, optionally at least 0.8% , Optionally at least 0.9%, optionally at least 1%, optionally at least 1.1%. In some embodiments of the present invention, the amount of crosslinker residue in the polymer is at most 2.7%, optionally at most 2.4%, optionally at most 2.1%, optionally at most 1.8%, optionally at most 1.5%. In some embodiments of the invention, the amount of crosslinker residue is from 0.7% to 3%, optionally from 0.9% to 2.8%, optionally from 1.2% to 2.7%; In these embodiments, the molecular weight of the crosslinker is 180 to 330, optionally 200 to 300. In some embodiments of the invention, the crosslinker is diethylenically unsaturated, for example a di (meth) acrylate ester of DVB, ALMA or diol. In some embodiments, the polymer comprises a diethylenically unsaturated crosslinking agent having a molecular weight ranging from 100 to 250, optionally from 110 to 230, optionally from 110 to 200, optionally from 115 to 160. In some embodiments of the invention, the crosslinker is unsaturated in triethylene form. In some embodiments of the invention, both triethylene type unsaturated crosslinkers and diethylene type unsaturated crosslinkers are present. In some embodiments of the present invention, the wt% of the crosslinking agent is in a range represented by (wt% x functionality / 2) / (MW / 130) of 0.2 to 1.7, wherein the functionality is ) Is the number of ethylenically unsaturated units in the crosslinking agent, and MW is its molecular weight. The factor indicates that crosslinkers with higher molecular weights (at the same functional group) are used at higher levels and crosslinkers with two or more functional groups (at the same molecular weight) can be used in smaller amounts. In some embodiments, the factor is at least 0.3, optionally at least 0.4, optionally at least 0.5, optionally at least 0.6, optionally at least 0.7, optionally at least 0.8, optionally at least 0.9, optionally at least 1. In some embodiments, the factor is 1.6 or less, optionally 1.5 or less.

In some embodiments of the invention, the aqueous coating composition comprises 10% to 25%, optionally 11% to 20%, optionally 12% to 18%, optionally 13% to 16% of the polymer. Percentages are calculated based on the amount of polymer solids in the total weight of the coating composition. In some embodiments, one or more polymers according to the invention may be present and the total amount of the polymers is within the range of the amounts described above.

In some embodiments of the invention, the polymers used in the present invention are known emulsion polymerization methods, and free radical initiators such as, for example, peroxygen compounds or diazo compounds, and optionally chain transfer agents. Is prepared by copolymerizing the monomers using any other suitable method known in the art. The length of the primary polymer chain is generally in the range of about 50,000 to 10,000,000, optionally 100,000 to 5,000,000, optionally 200,000 to 2,000,000, after crosslinking is removed.

Preferably, the polymer of the invention is an aromatic-acrylic polymer, more preferably a styrene-acrylic polymer. Preferably the aqueous coating composition comprises at least 45%, optionally at least 50%, optionally at least 55%, optionally at least 60%, optionally at least 65% of water. Preferably the aqueous composition comprises at most 10% organic solvent, optionally at most 8%, optionally at most 6%. In some embodiments, the composition comprises at least 2%, optionally at least 4%, optionally at least 4.5% of organic solvent.

The composition of the present invention may optionally include other components, for example waxes, alkali-soluble resins, plasticizers, wetting agents, antifoaming agents, soluble or dispersible insecticides, polyurethane dispersants, silicates and the like. In the present invention, the alkali-soluble resin is in the range of 0% to 10%, more preferably 2% to 7%. The wax is used in the range of 5% to 20%, more preferably 7% to 15%.

In the process of the invention, the aqueous composition is applied to surfaces such as, for example, floors, walls, counter tops, roofs. Materials to which the composition can be applied are stones, concrete, asphalt, ceiling materials, linoleum, tiles, wood, particle or fiber boards, glass, leather, paper and cardboard, and the like. In some embodiments of the invention, the composition is applied to the bottom. Preferably, the composition can be used as needed but cures under ambient conditions without external heating, ventilation or humidity control.

Floor gloss coating performance evaluation test

In order to properly evaluate the performance of an emulsion polymer for use as a gloss vehicle, the polymer must be formulated with a gloss agent. Formulation of the emulsion polymers of the present invention has been carried out by methods common and well known to those skilled in the art. The components used, their proportions and methods of addition are the same as those conventionally practiced with emulsion polymers of the general art. Ingredients used in formulated floor polishes include emulsion polymers, wax emulsions, alkali soluble resins (ASRs), film forming aids, leveling agents and wetting agents. The concentration of flocculant solvent, plastic solvent and leveling agent used in the formulation of the brightener is determined by the compatibility of the emulsion polymer (the overall composition of the polymer) with the selected solvent and additives and the minimum filming temperature of the emulsion polymer. do. For the emulsion polymers of the examples listed here, the concentrations of flocculant, plasticizer and additives are as given in the details of the formulation, with minimal adjustment appropriately so that each polymer embodiment forms a glossy, substantially coherent film. Was done.

Test Methods:

Various tests have been used in the present invention to evaluate the function of the emulsion polymer vehicle as a removable floor polish (or floor coating). The surface coatings were evaluated for gloss, leveling, tack-free time, gloss retention, soil resistance, black heel mark and scratch resistance, water resistance and detergent resistance. The test method used in the evaluation of the surface coatings of the present invention is a standard test method known to those skilled in the art. Further testing was also performed in the Accelerated Wear Tester (AWT). AWT is described in US Patent Application Publication No. 2008/0000285. AWT simulates wear and retention when exposed to conventional floor coatings in an accelerated manner. Test methods were conducted at AWT, which is associated with wear and maintenance conditions when typical floor polishes were exposed on site. AWT has equipment to measure and record gloss and color. The following test method was used to evaluate the performance of the emulsion polymer vehicle, which is the subject of the present invention.

Coating work to evaluate the bench characteristics of an aqueous floor coating composition :

The method of applying the bottom gloss coating to a substrate for testing purposes is described in "Annual Book of ASTM Standards," Section 15, Volume 15.04, Test Procedure ASTM D 1436 (200), Test Method B. As detailed in the tests reported below, floor polishes were applied to vinyl composition tiles or vinyl tiles according to the formulation of Tables (6, 13, 17, 20, 23, 26, 32, 35, 38, 41, 46). Was applied by coating 2 to 5 times. The bottom coating was coated at about 30-60 minute intervals or applied as detailed in each test and the coated panel cured at ambient conditions for 24 hours or as detailed in the test.

Design of gloss test method :

The test was carried out on black vinyl composition tiles (BVCT). This method used to measure gloss is described in "Annual Book of ASTM Standards", Section 15, Volume 15.04, Test Procedure ASTM D 1455. 20 ° gloss and 60 ° gloss were recorded using a Gardner Byk Micro-triGloss meter. The gloss thus measured is also referred to as quantitative gloss. Gloss evaluation was performed on 4 to 5 finish coatings and compared to the control finish. Gloss was measured after each applied coating had dried and before applying the next coating of floor polish. It was also measured the next day (16 to 24 hours after the final coating was applied). Glossiness was reported in tabular form. As can be seen, the coated tiles were also evaluated; This is called qualitative gloss. Gloss was rated as a rating of 1 to 5 as follows: 1 = bad; 2 = normal; 3 = good; 4 = very good; 5 = excellent

Leveling test method :

This test was performed on black vinyl tiles (BVT) and / or (BVCT). Immediately after the floor varnish was applied to the tile, "X" was drawn diagonally from corner to corner of the test area with a gauze pad application tool and marked on the wet polished surface. This can also be done with a mop when the test area is a floor test. After the film was dried, the coating was visually tested to determine the degree of loss of the "X". Leveling was rated as follows with a rating of 1 to 5:

1 = bad, there is a contour of the "X" ridge and a clear dewetting; 2 = normal, flat contour and dent of "X" is detected; 3 = good, flat contour of "X" is detected but dents are lost; 4 = very good, a faint outline of "X" is detected and the dents are also lost; 5 = Excellent, "X" not detected.

Tack free time test method :

The tack free time of the surface coating was measured using a Zapon tack tester. The tack tester was made from a 1 inch wide vent piece of aluminum sheet metal 1/16 inch (1.6 mm) thick. This was made so that the 1 in ² (2.54 cm) section was left exactly on the surface. The weight was given so that the strip stood up when the weight was 5 grams in the center of the aluminum strip. If a weight less than 5 grams is placed in the center of the aluminum strip, the strip will fall off. The tack tester was placed on the surface of the film and a 500 gram weight was placed on the tester. This weight was kept in the tester for 5 seconds and then removed. The coating was considered tack free if the tester was stopped within 5 seconds. The elapsed time from when the coating was applied to the tack free time point was evaluated in grades 1 to 5 as follows: 1 = bad, Zapon tack free time of at least 45 minutes; 2 = normal, Zapon tack free time of 39 to 45 minutes; 3 = good, Zapon tack free time from 32 to 39 minutes; ; 4 = very good, Zapon tack free time of 25 to 32 minutes; 5 = Excellent, Zapon tack free time of 18 to 25 minutes

1 hour water resistance test :

A one hour water resistance test was performed on BVCT coated three or more times with the test finish. The coating was dried for 16 to 24 hours before running the test. Circles (about 1 inch in diameter {2.54 cm}) were drawn during the dry coating with a China marker. A circle of 3 to 5 finish coatings was filled with a drop of clean water. The droplets were left at ambient temperature for 60 minutes. After 60 minutes, the area was wiped off with a dry tissue to remove water stains. The circle was then evaluated for discoloration or damage to the film. 1 hour water resistance was rated as a grade from 1 to 5 as follows: 1 = bad, film removal of 25% or more; 2 = normal, 16-25% film removal; 3 = good, 6-15% film removal; 4 = very good, slight gloss reduction and / or less than 5% film; 5 = Excellent, no water stains or damage.

Next day water resistance test method :

This test is similar to the one hour water resistance test. The only difference is that the bottom coating is left for 16 to 24 hours before dropping the water drop onto BVCT. The next day water resistance was rated as a grade from 1 to 5 as follows: 1 = bad, film removal of at least 16%; 2 = normal, 11-15% film removal; 3 = good, 6-10% film removal; 4 = very good, slight gloss reduction and / or less than 5% film; 5 = Excellent, no water stains or damage.

Alkaline detergent resistance test method :

BVCT was coated three or more times with the test finish. The coating was dried for 16 to 24 hours before running the test. Circles (about 1 inch in diameter {2.54 cm}) were drawn during the dry coating with a China marker. Droplets of diluted alkaline floor cleaners (GP FORWARD, Johson Diversey) were filled in circles in contact with the finish coating 3 to 5 times. The detergent drops were left at ambient temperature for 30 minutes. After 30 minutes, the area was wiped off with a dry tissue to remove water stains. The circle was then evaluated for discoloration or damage to the film. Alkaline detergent resistance was rated as a grade from 1 to 5 as follows: 1 = bad, film removal of at least 50%; 2 = normal, 25-50% film removal; 3 = good, 10-25% film removal; 4 = very good, slight gloss reduction and / or less than 10% film; 5 = Excellent, no water stains or damage.

1 hour neutral detergent resistance test method :

BVCT was coated three or more times with the test finish. This test was performed after applying the final coating of finish and drying the coating for 1 hour. Circles (about 1 inch in diameter {2.54 cm}) were drawn during the dry coating with a China marker. A circle of 3-5 contact finish coats was filled with drops of diluted neutral floor cleaner (STRIDE, available from Johson Diversey). The detergent drops were left at ambient temperature for 30 minutes. After 30 minutes, the area was wiped off with a dry tissue to remove water stains. The circle was then evaluated for discoloration or damage to the film. Alkaline detergent resistance was rated as a grade from 1 to 5 as follows: 1 = bad, film removal of at least 50%; 2 = normal, 25-50% film removal; 3 = good, 10-25% film removal; 4 = very good, slight gloss reduction and / or less than 10% film; 5 = Excellent, no water stains or damage.

Next day neutral detergent resistance test method :

This test was performed in BVCT coated three or more times with the test finish. The coating was dried for 16 to 24 hours before running this test. Circles (about 1 inch in diameter {2.54 cm}) were drawn during the dry coating with a China marker. A circle of 3-5 contact finish coats was filled with drops of diluted neutral floor cleaner (STRIDE, manufactured by Johson Diversey). The detergent drops were left at ambient temperature for 30 minutes. After 30 minutes, the area was wiped off with a dry tissue to remove water stains. The circle was then evaluated for discoloration or damage to the film. Neutral detergent resistance was rated as grades 1-5 as follows: 1 = bad, 50% or more film removal; 2 = normal, 25-50% film removal; 3 = good, 10-25% film removal; 4 = very good, slight gloss reduction and / or less than 10% film; 5 = Excellent, no water stains or damage.

Black heel mark and scratch resistance test method :

A two coat of finish was applied to a 12 "(30.5 cm) x 12" tile at CTR (75 ° F {77 ° C}, 50% humidity). The tiles were aged for 24 hours before starting the test in CTR. Marks were generated by driving in each direction (forward and reverse) for 10 minutes at 50 rpm in a Snell Capsule equipped with six black rubber hills. The tiles were separated and compared to the control finish on the control tile. The tiles were evaluated visually. Black heel marks and scratch resistance were evaluated as grades 1 to 5 as follows: 1 = bad, severe marks scattering; 2 = moderate, moderate to severe scatter of marks; 3 = good, moderate mark spread; 4 = very good, slightly to moderate mark spread; 5 = excellent, slight mark spread

Wear resistance test method :

The wear resistance test is conducted by striking the coating with a hard object at an angle of less than 45 °; In the examples provided, the nails of the individual performing this test with the object were used. This test provides an indication of how the coating withstands damage and thus reduces the gloss of the coating. After the coating was applied to the substrate and cured, the coated substrate was placed on a solid surface, such as a table top, and scratched with the fingernails of the tester. The tester's nails were parallel to the coated surface and the impact angle was at least 45 ° to the normal of the surface, causing more scratches on the coating. When comparing coatings, it is important that the same tester performs the test. This test is designed so that relative differences are evident. Abrasion resistance was rated as a grade from 1 to 5 as follows: 1 = bad, very pronounced and deep scratch presence; 3 = good, recognizable scratch presence; 5 = excellent, almost undetectable scratch

Accelerated Wear Test method of gloss retention using Tester ( AWT ) :

The method of applying the bottom gloss coating to a substrate for testing purposes is described in "Annual Book of ASTM Standards," Section 15, Volume 15.04, Test Procedure ASTM D 1436 (200), Test Method B. The finish was coated four times on the substrate with a drying time of about 30 to 60 minutes between coatings. The coating was applied in a constant temperature room maintained at 75 ° F. ± 5 ° F. and a relative humidity of 50% ± 5%. The preferred substrate for gloss retention testing is BVCT. An important property evaluated is gloss retention. After the fourth coating, the coating was fixed for about 16 to 24 hours before testing with AWT. A gloss meter as described above was placed on a "robotic" arm that measured numerically through the control program of AWT and measured and recorded the gloss of the coated substrate.

AWT settings are described in US Patent Application Publication No. 2008/0000285 A1 and were used to impose wear on the coating being tested. The sequence of steps shown in Table 1 was performed in sequence every cycle. The cycle is completed after the end of step 12. The cycles were then repeated to establish a series of wear and maintenance steps. Initial gloss data corresponds to gloss measurements prior to any treatment or maintenance. Gloss was generally measured every five cycles. This plots the performance against the number of cycles, where the cycle number is related to time. The following multistage wear profiles listed in Table 1 were performed. This experiment ran between 50 and 150 cycles. Final gloss was measured at least after the end of the cycle.

AWT High Maintenance Wear Profile step designation Action One Gloss measurement 20 ° and 60 ° gloss measurements 2 Color measurement L * a * b * measurement (reflectivity, non-contact) 3 Dirt Sediment of synthetic soil on BVCT by passing the tiles under the soil hopper 4 Soil Grind the synthetic soil by passing the coating seven times through a 30 psig roller 5 vacuum Vacuuming out of the soil 6 Wetting Wet the tiles with water from the spray nozzle to minimize dust 7 washing Two double passes through automatic scrubber with neutral floor cleaner 8 Waiting Wait 15 minutes for automatic scrubber drying 9 dry Pass the tile under an air knife for 5 minutes to dry the coating 10 Burnishing Glossy recovery by passing the tile through the burner twice (burns pad at 1500 rpm) 11 dry Double pass through air knife once to remove remaining dust 12 Waiting Wait 15 minutes to recover coating Return to step 1 or 3 and repeat

Gloss Measurement :

The gloss value measured and recorded is the average value of gloss (20 ° gloss and 60 ° gloss) measured 6 to 8 times. AWT measured and recorded the gloss value. Initial gloss measurements (zero cycles) were recorded by AWT before performing the wear phase. This should be well correlated with the gloss value over the next day. Gloss retention was determined by evaluating measured quantitative gloss values and visual qualitative gloss by comparing the initial gloss value at the end of the experiment. The results were then compared with a control finish conducted under the same high retention wear profile. Gloss retention was rated as 1-5, as follows: 1 = bad, complete film separation, final gloss substantially below initial gloss; 2 = medium, medium film separation, final gloss less than initial gloss: 3 = good, partial film separation, final gloss similar to initial gloss; 4 = very good, slight film separation, final gloss better than initial gloss; 5 = Excellent, film fixation, final gloss is substantially better than initial gloss

Soil Tolerance Using AWT Test Method :

This test was performed according to the coating application method described above using white vinyl composition tiles (WVCT). Four coats of the bottom coating were performed at CTR (75 ° F. ± 5 ° F. and 50% ± 5% relative humidity) and the coating was fixed for 16-24 hours prior to the AWT run. The main characteristic evaluated is color change. In the AWT wear profile, a series of steps listed in Table 2 were performed in sequence. The cycle is completed after ending step 11. The cycle was then repeated to establish a series of wear and maintenance steps. Color was measured every cycle. This plots the performance against the number of cycles, where the cycle number is related to time. The following multistage wear profiles listed in Table 2 were performed. This experiment ran from 10 to 40 cycles.

AWT Soil Resistant Abrasion Profile step designation Action One color L * a * b * measurement (reflectivity, non-contact) 2 washing 5 double passes through automatic scrubber with antiseptic floor cleaner 3 Waiting Wait 15 minutes to dry the scrubber 4 dry Dry the coating by passing the tiles under an air knife for 10 minutes 5 Dirt Sedimentation of synthetic soil in WVCT by passing tiles under soil hopper 6 damage Grind the synthetic soil by double-coating 10 passes through a 30 psig roller 7 vacuum Vacuuming out of the soil 8 Wetting Wet the tiles with water from the spray nozzle to minimize dust 9 washing Single pass through automatic scrubber with bactericidal floor cleaner 10 Waiting Wait 15 minutes to dry the scrubber 11 dry 1 double pass through air knife to remove remaining dust Go back to step 1 or 2

Color measurement:

AWT color results were reported in the L * a * b * color space. The color was measured using a VeriColor Spectro VS410 non-contact spectrophotometer (X-rite Inc) fixed to an "robotic" arm. The non-contact spectrophotometer and the "robotic" arm are controlled by an AWT control program. The color of each floor finish was measured and recorded by AWT at 12-16 different locations on the coated WVC tile. The color change was determined using the average of L * a * b * values. The ΔE * color change results were determined by Equation 1 below, where the final measured color was compared with the initially measured color. As defined, the color measured in cycle 0 is the initial color data. This color corresponds to the color of the next day. The final color measurement after the last cycle is defined as the final color measurement.

ΔE * = ((L ^* ₁ -L ^* ₂ ) ² + (a ^* ₁ -a ^* ₂ ) ² + (b ^* ₁ -b ^* ₂ ) ² ) ^0.5 (1)

Floor polish performance floor test in grocery store :

The remaining polish was wiped off from the floor test area and then repolished with the usual cleaning procedure as follows: mop the floor to remove dust and 1 liter per 4 liters of an aqueous solution of a commercially available cleaning solution (FREEDOM, Johnson Diversey Inc) Is applied with a mop at a rate of about 1,000 ft ² per gallon, soaked for 5 minutes, then the floor is rubbed with a propane stripping machine (SIDEWINDER, manufactured by AZTEC Inc), mopped with clean water and rinsed thoroughly. It was washed with an automatic scrubber (PE-1700 autoscrubber from Pioneer Eclipse Inc) using a blue cleaning pad (Blue Cleaner Pad 5300, manufactured by 3M Company), and the floor was rinsed once more with clean water and then dried. The cleaned floor was divided into sections perpendicular to the normal direction of the floor passage. Each section was coated with the test formulation four times with a finishing mop at a rate of about 2,000 ft ² per gallon. Each coating was dried for 30 to 60 minutes before the next coating was applied. Coating (four coats) was carried out on the floor consisting of a homogeneous vinyl composition tile and cured at ambient temperature.

After the coating had cured at ambient conditions, the floor was opened to pedestrians. The floor test area was exposed not only to pedestrians (about 25,000 per week) but also to wheeled vehicles such as shopping carts, carts, loading carts, and sample trays. After sufficient exposure to the passage, 20 ° gloss and 60 ° gloss were measured every 5-10 days, and automatic scrubbing and glossing of the machine with a neutral floor cleaning solution for the test floor was carried out by the general cleaning method as follows: The dust was removed by mopping, and the floor was mechanically wiped with a Pioneer Eclipse PE-1700 Automatic Scrubber equipped with a 3M Red Cleaner Pad 5200. The cleaning solution filled in the Pioneer Eclipse PE-1700 Automatic Scrubber is a dilution rate Stride neutral floor cleaner from Johnson Diversey. The 2,000 rpm propane burnishing machine used was the SpeedStar Pioneer ST21K WA (Pioneer Eclipse, Sparta NC). The SpeedStar propane burners were equipped with a 21 inch 3M 3200 TopLine Speed Burnish Pad. The test floor was passed through an automatic scrubber and burnishing machine twice three to five times weekly for 15 weeks.

Example

Example  1: Preparation of Latex Polymer

In a suitable reaction vessel equipped with a thermometer, condenser and stirrer, a solution of 25.90 g of 23% sodium dodecylbenzene sulfonate (POLYSTEP A-16-22, Stepan Company), 13.74 g of itaconic acid and 700.1 g of deionized water was Heated to ° C. 14.43 g of the monomer emulsion described in Table 3 were added to the reaction vessel at once and the temperature was adjusted to 80-85 ° C., and then ammonium persulfate (APS) catalyst solution (3.15 g dissolved in 14.00 g of water) was added to the vessel. Charged. Within 2 minutes, the initiation of the polymerization reaction was indicated by a temperature rise of 3-5 ° C. and a change in state (color and opacity) of the reaction mixture. When the exotherm ceased, the catalyst solution (0.61 g APS in 100 g deionized water) co-fed with the remaining monomer mixture was slowly added to the reaction vessel at about 85 ° C. for 90 minutes (addition time is preferably 90 to 120 minutes). ). Termination after 15 minutes of feeding; The vessel was cooled to 60 ° C., followed by 1.48 g of 0.15% iron (II) sulfate dissolved in 5 g of water, 0.61 g of 70% t-butyl hydroperoxide and 8.6 g of dissolved in 8.6 g of water. 0.30 g isoascorbic acid dissolved in water was added. The second step, after 15 minutes, consists of 0.61 g of 70% t-butyl hydroperoxide dissolved in 8.6 g of water and 0.30 g of isoascorbic acid dissolved in 8.6 g of water. After 25 minutes, the latex was cooled to 39 ° C. and 17.00 g of 70% polyoxyethylene lauryl alcohol (Thorcowet TDA-40, Thornley Company) dissolved in 35.6 g of water was added to the latex and stirred for about 10 minutes. It was. The pH of the latex was adjusted to 6.7 by adding 30.0 g of 10% ammonium hydroxide for about 15 minutes. After holding for 5 minutes, a slurry of 9.73 g of calcium hydroxide and 5 g rinse dissolved in 22.7 g of water was added to the vessel and stirred at 39 ° C. for 1 hour to yield 0.270 equivalents of calcium. The concentration of polyvalent metal ions is a function of the carboxylic acid functional group content of the polymer. The latex was cooled and filtered to produce a denatured latex comprising 0.27 equivalents of calcium. The latex comprises a polymer of 23.5 BA / 30.1 MMA / 34.2 styrene / 9.0 MAA / 1.9 IA / 1.3 DVB / 0.27 equivalents Ca and the measured Tg is 83 ° C. Thereafter, water was added to bring the solid concentration to 38%.

matter Parts by weight 208.5 g water 13.84 g POLYSTEP A-16-22 (23%) (Sepan Company) 171.76 g Butyl Acrylate (BA) 23.5 250.19 g Styrene 34.2 219.92 g Methyl methacrylate 30.1 65.7 g Methacrylic acid (MAA) 9.0 9.38 g Divinylbenzene (DVB) 1.3

The itaconic acid (13.74 g, 1.9%) was added directly to the container and is not part of the monomer emulsion.

Example  2 to 5

Prior Art References US Pat. No. 6,586,516 and US Patent Application Publication No. 2007 / 0254108A1 describe polymer compositions that are similar but not identical to the present invention. While the prior art describes the use of covalent and ionic crosslinks in acrylic polymer compositions, it does not describe suitable polymer formulations that exhibit acceptable performance with calcium and / or magnesium. Examples 1-5 show a comparison of the present invention with the prior art described in US Pat. No. 6,586,516 and US Patent Application Publication No. 2007 / 0254108A1.

A series of styrene-acrylic polymer dispersions were prepared from monomer emulsions containing the monomer ratios listed in Table 4 by the conventional stepwise addition method described in Example 1. The latex compositions of Examples 2-5 are comparative and prepared according to the methods described in the prior art references US Pat. No. 6,586,516 and US Patent Application Publication No. 2007 / 0254108A1. Tg of typical polymers is reported in Table 5 as measured by DSC described above. Tg of Comparative Examples 2 to 4 is in the range of -37 ° C to 75 ° C in the prior art. The average Tg of Example 1, 1st, and 2nd heating is 83 degreeC.

Floor coating composition:

All performance tests described below were performed on formulated coating compositions. The components used to formulate the coating compositions are shown in Table 6. Performance results are listed in the following table.

Example polymer
solid Monomer composition metal Eq. Crosslinking agent X-link
wt% Add.
comp.
mon. Comp.
wt% One 38% 1.9IA / 23.5BA / 30.1MMA /
34.2Sty / 9.0MAA / 1.3DVB Ca 0.27 DVB 1.3 IA 1.9 2 34% 2.5IA / 6MAM / 30EA / 57.5EHA / 4M
AA / 0.08ALMA Zn 0.40 ALMA 0.08 IA 2.5 3 35% 2.5IA / 6MAM / 30EA / 57.5EHA / 4M
AA / 0.08ALMA Ca 0.18 ALMA 0.08 IA 2.5 4 38% 18BA / 50MMA / 20AAEM / 12MAA Ca 0.23 AAEM 20 none 0.0 5 37% 24BA / 43MMA / 20AAEM / 5Sty / 8
MAA Mg 0.28 AAEM 20 none 0.0

AAEM = acetoacetoxyethyl methacrylate = potential crosslinker

Eq. = Equivalent of metal ions per total complexing functional group in the emulsion polymer

X-link wt% = weight percent of crosslinker in the emulsion polymer

Add. comp. mon. = Complexing monomers other than MAA

Comp. wt% = weight% of complexing monomers other than MAA

Evaluation of Coating Gloss:

20 ° and 60 ° gloss measurements are listed in Table 7. Formulation 1A showed the best next day gloss for both 20 ° and 60 ° gloss.

Tack Free Time:

The tack free time was measured using the zapon test and the test method was as described above. The results reported in Table 7 are the time required to pass the zapon test in minutes. Examples 1, 4 and 5 showed acceptable tack free times. Examples 2 and 3 were not tack free even after 48 hours.

Next day water resistance test:

Surface coating resistance to water damage was determined by the next water resistance test, the method as described above. The test results are shown in Table 7.

Comp. Comp. Comp. Comp. Formulation 1A 2A 3A 4A 5A 20 ° gloss measurement 4th coating 61 55 51 14 51 Next day 45 44 41 13 41 60 ° gloss measurement 4th coating 85 82 79 43 80 Next day 81 77 74 44 75 Average tack time ≥25 minutes > 48 hours > 48 hours 16 minutes 17 minutes Water resistance 5 4 5 3 4

Gloss retention test using AWT:

Gloss surface coating retention was measured using AWT. 20 ° gloss retention results are included in Table 10. Surface coating retention results of 60 ° gloss are listed in Table 11. Formulation 1A showed the best gloss retention at the end of the test in AWT, and the control formulations 2A, 4A and 5A of the comparative examples failed this test.

Comp. Comp. Comp. Comp. Formulation 1A 2A 3A 4A 5A Initial 20 ° Gloss 35 33 NA ^* 17 38 Final 20 ° gloss 40 40 NA ^* 10 19 Gloss change rate 14% 21% NA ^* 41% 50% Gloss retention Great Great NA ^* Bad Bad Initial visual shine Very good Poor (stripes) NA ^* Bad Very good Final visual shine Very good Poor (stripes) NA ^* Remove film Remove film

The tackiness of this coating interfered with the measurement by AWT.

Comp. Comp. Comp. Comp. Formulation 1A 2A 3A 4A 5A Initial 60 ° Gloss 76 76 NA 52 76 Final 60 ° gloss 75 75 NA 35 52 Gloss change rate -1.3% 1.3% NA 33.0% 32.0%

Example  1 to 6

A series of styrene-acrylic polymer dispersions were prepared from monomer emulsions containing the monomer ratios listed in Table 12 by the conventional stepwise addition method described in Example 1. Example 6 is a comparative comparative example that does not contain DVB. The coating composition of Example 6 was gloss tested and compared with the coating composition of Example 1. The ingredients used to prepare the latex into fully formulated floor polishes are listed in Table 13.

Performance tests were conducted at the grocery store, where the floors were regularly machine maintained, subject to actual conditions, for the fully formulated coating compositions described in Table 13. The floor was dry mop every evening (7 days per week) and mechanically managed (4-5 times per week) with an automatic scrubber using a neutral floor cleaner and a red cleaning pad, followed by propane burnishing with 3200 burnish pads. The gloss measurements were recorded regularly for 15 weeks for the brighteners listed in Tables 14 and 15.

The 20 ° gloss measurement results are reported in Table 14. The 60 ° gloss value obtained in the field test is shown in Table 15. Comparison of Formulation 1B and Formulation 6A indicates that gloss retention is improved in the emulsion polymers comprising covalent crosslinker DVB. Formula 1B retained its 20 ° gloss in field trials, while Formulation 6A lost 20 ° gloss. In the field trials both examples lost 60 ° gloss during the 15 week test period. However, it should be noted that Formulation 1B has a 60 ° gloss loss less than Formulation 6A.

Eq. = Equivalent of metal ions per total acid functional group in the emulsion polymer

Example  7 to 10

A series of styrene-acrylic polymer dispersions were prepared from monomer emulsions containing the monomer ratios listed in Table 12 by the conventional stepwise addition method described in Example 1. In the above examples, phosphoethyl methacrylate was used as an additional complexing monomer and the specific monomer tested was ethyl methacrylate phosphate (SIPOMER PAM 4000 (PAM), RHODIA Inc).

The components of the fully formulated floor polish are listed in Table 17. Floor polish 7A is a comparative example and is an emulsion polymer containing zinc crosslinks. The performance of Formulations 7A, 8A, 9A and 10A was tested and the results are shown in Table 18. The fully formulated polymers, formulations 8A, 9A and 10A, have essentially the same performance as the comparative Comparative Formulation 7A containing zinc.

SCOF = static coefficient of friction measured by James test

The ratings range from 5 (highest) to 1 (lowest).

Example  11 to 13

A series of styrene-acrylic polymer dispersions were prepared from monomer emulsions containing the monomer ratios listed in Table 12 by the conventional stepwise addition method described in Example 1. Example 7 is a comparative example and is a zinc crosslinked emulsion polymer.

Performance tests were conducted on fully formulated floor polishes, the components of which are listed in Table 20 and the results reported in Table 21. The performance of the floor polish based on Example 13 was better than Control Example 7 containing zinc. The covalent crosslink concentration of Example 13 was 1.7 wt%. Two other test finishes examples 11 and 12 had essentially comparable results to zinc control finish example 7.

Example  14 to 20

A series of styrene-acrylic polymer dispersions were prepared from monomer emulsions containing the monomer ratios listed in Table 12 by the conventional stepwise addition method described in Example 1. Example 7 is a comparative example and is a zinc crosslinked emulsion polymer.

Performance tests were conducted on fully formulated floor polishes, where the floor polish example components are listed in Table 23 and the results are listed in Table 24. Formulation 16A had the best gloss over the next day; The tack free time was longer than other formulations. Formulation 17A has essentially comparable performance to the comparative Comparative Formulation 7A containing zinc.

Example  21 to 28

A series of styrene-acrylic polymer dispersions were prepared from monomer emulsions containing the monomer ratios listed in Table 12 by the conventional stepwise addition method described in Example 1. Examples 21, 22 and 23 are comparative emulsion polymers. Performance tests were conducted on fully formulated floor polishes, wherein the components of the formulations are listed in Table 26. The floor polish was tested for AWT in addition to the standard bench test. Bench and AWT results are reported in Table 27. Formulations 26A, 27A and 28A had essentially comparable gloss retention as measured by AWT. The comparative Comparative Formulation 22B exhibited the best gloss retention among the series as measured by AWT. Formulations 25B, 26A, 27A, 28A outperformed comparative formulations 21A, 22B and 23A in soil resistance as measured by soil resistance using the AWT test method.

Example  32 to 36

A series of styrene-acrylic polymer dispersions were prepared from monomer emulsions containing the monomer ratios listed in Table 12 by the conventional stepwise addition method described in Example 1. Control Comparative Latex is Example 29, which is a zinc crosslinked emulsion polymer. Performance tests were conducted on fully formulated floor polishes, wherein the components of the floor polish examples are listed in Table 32. The test results are reported in Table 33. The emulsion polymer of Example 32 had better performance than Examples 31 and 30. The (variable) factor evaluated in the series of experiments described above is the amount of Ca. The calcium content varied from 0.28 eq to 0.58 eq based on the total acid monomer content. Increasing the calcium content increases the crosslink density, improves scratch, damage and scratch resistance and improves its durability.

Floor coating 29A 32C 34C 35C 36C Complexing monomer IA IA IA IA metal Zn Ca Ca Ca Ca Wear resistant 5 3 3 5 5

Example  37 to 41

A series of styrene-acrylic polymer dispersions were prepared from monomer emulsions containing the monomer ratios listed in Table 12 by the conventional stepwise addition method described in Example 1. Control Comparative Latex is Example 29, which is a zinc crosslinked emulsion polymer. Performance tests were conducted on fully formulated floor polishes and the components are listed in Table 35. The test results are reported in Table 36.

Example  42 to 44

A series of styrene-acrylic polymer dispersions were prepared from monomer emulsions containing the monomer ratios listed in Table 12 by the conventional stepwise addition method described in Example 1. Control Comparative Latex is Example 29, which is a zinc crosslinked emulsion polymer. Performance tests were conducted on fully formulated floor polishes and the components are listed in Table 38. The test results are reported in Table 39.

The amount of Ca was fixed at 0.58 equivalents Ca based on the total acid. Variables in this series are the Tg and acidic monomer content of the polymer. Acidic monomers evaluated in this series are MAA, IA and AA (acrylic acid). Total acidity was maintained at 14 wt%. MAA was replaced with IA, AA or a mixture of IA and AA. The Tg of the polymer was adjusted by changing the BA / MMA content of the polymer.

Example  45

The monomer types and concentrations of Example 45 are reported in Table 12. Performance tests were conducted on fully formulated floor polishes and the components are listed in Table 41. The test results are reported in Table 42. The composition of Example 45 comprises magnesium (0.28 equivalents based on total acidic monomers).

Example  46

The latex preparation method of Example 46 was described in Example 1 except that the monomer types and concentrations are reported in Table 12. Control Comparative Latex is Example 29, which is a zinc crosslinked emulsion polymer. Performance tests were conducted on fully formulated floor polishes and the components of the floor polish example are listed in Table 43. The test results are reported in Table 44. The composition of Example 46 was crosslinked with Ca (0.28 equivalents based on total acidic monomers) and BGDMA.

Claims (10)

(a) at least one of calcium ions and magnesium ions; (b) (i) 0.5 to 7 wt% of at least one monomer having an exponential stability constant of 0.3 to 4 for calcium or magnesium; (ii) 5 to 15 wt% methacrylic acid; And (iii) a polymerized moiety consisting of 0.2 to 3 wt% of at least one crosslinking agent and comprising a polymer having a Tg of 50 to 110 ° C. The aqueous coating composition of claim 1 comprising calcium ions. The polymer composition of claim 2, wherein the polymer comprises (i) 1 to 6 wt% of at least one monomer selected from the group consisting of acrylic acid, itaconic acid and phosphoethyl methacrylate; (ii) 6 to 13 wt% methacrylic acid; (iii) 0.5 to 2.7 wt% of at least one crosslinker; And (iv) a polymerized moiety consisting of 25 to 45 wt% of one or more vinyl aromatic monomers; Wherein the polymer has a Tg of 60 to 100 ° C. 4. The aqueous coating composition of claim 3, wherein the polymer comprises polymerized moieties of crosslinking agents unsaturated in diethylene form. The method of claim 4, wherein the complexing monomer is selected from the group consisting of acrylic acid and itaconic acid; Wherein said at least one vinyl aromatic monomer comprises styrene. The aqueous coating composition of claim 5, wherein the polymer further comprises 38 to 64% polymerized residues of C ₁ -C ₈ alkyl (meth) acrylate. 6. The aqueous coating composition of claim 5 wherein the molecular weight of the diethylenically unsaturated crosslinker is from 100 to 250. 7. The aqueous coating composition of claim 6, wherein the polymer comprises polymerized moieties of 0.8-1.8 wt% of a diethylenically unsaturated crosslinker. The method of claim 8, wherein the polymer comprises 0.2 to 0.6 equivalents of calcium per equivalent of acid monomer, and (i) 1.3 to 4 wt% of at least one monomer selected from the group consisting of acrylic acid and itaconic acid; (ii) 7-12 wt% methacrylic acid; (iii) 0.8 to 2.4 wt% of a crosslinking agent unsaturated in diethyl form; (iv) 30 to 40 wt% styrene; And (v) a polymerized moiety consisting of 44 to 62% of polymerized moieties of C ₁ -C ₈ alkyl (meth) acrylate. 10. The aqueous coating composition of claim 9, wherein the C ₁ -C ₈ alkyl (meth) acrylate comprises methyl methacrylate and butyl acrylate.